Ammonium salt production



Aug. 21, 1945. w1 mm' I AMMONIUM SALT PRODUCTION Fild uns 18. 1942' 2 snveetssheet 1 Aug. 2l, 41945. i w, T|DDY A 1 2,383,171

AMMONIUM SALT PRODUCTION Filed June 18. 1942 `:a sheets-sheet 2 'Il I 5w arawelf'zc (onderwerfalrazfar ATTORNEY Patented Aug'. 2.1,' 1.945

T 4UNITED STATES f PATEN'r OFFICE AMMONIUM sam PRODUCTION William Tldy, New-York, N. Y., assignor to Semet-Solvay Engineering Corporation, New York, N. Y., a corporation of New York applicati@ June 1s, 1942, serial No. 447,497

a claims. (o1. ca -119) This invention relates to the removal `of am- 'monia from coke oven gas 4and more particularly to the recovery of ammonia as ammonium salts from gases produced in the carbonization of coal,-

especially coke oven gas.

The customary practice followed for many' years in the recovery of ammonia from coke oven gas has involved drawing the gas by means of an exhauster through one or more packed cooling columns, and forcing the gas by the exhauster througha saturator containinga deep body of aqueous sulfuric acid saturated with ammonium sulfate whereby the ammonia present in the gas reacts with the acid to form ammonium sulfate which immediately separates from the solution in monium salt crystalsof relatively large uniform size from ammonia-containing gas produced in the carbonization of coal.

It is another object of the invention to provide a process of producing relatively large crystals oi ammonium salts, particularly ammonium sulfate from coke oven gas, which lprocess may be carthe form of small crystals containing a large pro' e portion of lines of almost powdery character; the

ammonium sulfate is removed from the saturator Jing and supersaturating under vacuum the salt and dried, e. g., by centrifuging. This process is subject to the disadvantage that owing to the small size and non-uniform character of the ammonium sulfate crystals they show a marked tendency to cake when stored.

My co-pending application Serial No. 358,233, led September 25, 1940, discloses a radically different, commercially successfully process for the recovery of ammonium sulfate from coke oven gas as relatively large uniform crystals by intimately contacting coke oven gas of controlled temperature and humidity with an unsaturated solution from the saturator, a crystallizi'ng cham-f ber in which the supersaturated solution is Vpassed into contact With previously formed crystals of the salt causing them to grow until they reach the desired size, and means for recirculating salt solution from the saturator to the vacuum chamber, thence to the crystallizing chamber and from the crystallizing chamber back to the saturator. The invention may be utilized in connection with conventional coke oven apparatus involving an exhausting pump driven by a condensingl steam engine and exhaust steam from the engi-ne may becondensed in a barometric condenser, together with the vapors from the vacuum chamber.

In carrying out the.proce'ss of `the invention, coke Oven gas containing ammonia preheated to a temperature of from 30 to 60 C. and at a regulated humidity within the range 'of 70 to 100 per cent is passed into a saturator beneath the suruum, passing the supersaturated solution into solution'with additional sulfuric acid through the scrubbing column. In order to practice this process in existing-coke oven plants equipped with saturator-type apparatus, it is necessary to replace the saturators with scrubbing columns and crystallizing apparatus. The present invention ammonium salt of aconcentration about or someis in the nature of an improvement on the invention of application Serial No. 358,233, whichim-4 l movement permits utilization of existing saturator-type equipment in the productionof large uniform crystals of ammonium salts such as arnmonium sulfatefrom coke oven gas.

It is an object'oi.' this invention to provide a' novel combination of saturator and crystallizing equipment for the recovery of ammonia as amface of a body of aqueous solution of a mineral acid, preferably sulfuric acid, containing an am-- moniumsalt of the acid in amount insuilicient to saturate the solution so that the ammonia in the gas reacts with the free acid and forms additional salt, while maintaining suflicient circulation within` the saturator to prevent excess local supersaturation with consequent crystal formation4 in the solution therein.' The resultant solution of what below saturation -is withdrawn from lthe saturator, evaporatively cooled and concentrated under vacuum in the vacuum'chamber to a condition of metastable supersaturation with respect to the salt and is then passed into contact with al' bed or suspension of crystals of the salt, whereby salt crystallizes from the solution on the surfaces of the crystals so that large crystals are formed.

The crystals settle to me bottom ci the suspenacid is then recirculated back to the saturator for the absorption oiV additional ammonia and the formation o! additional salt. Instead oi-sulfuric acid, other mineral acids such as nitric, phosphoric and hydrochloric acids may be employed.

The temperature and humidity of the coke oven gas entering the 'satura-iter, the rate of introductionof water and the rate of circulation of solution from the saturator to the crystallizing apparatus back to the saturator are correlated to evaporate approximately sucient water in the saturator to maintain the volume and temperature of the solution therein substantially constant and to provide a concentration of ammonium salt-in the solution withdrawn from the saturator at or somewhat below that required for saturation of the solution and below that at which substantial crystal formation would occur. The

' free acid content ofthe saturator solution is preierably maintained relatively low, i. e., within the vrange of from 1 to 5 per cent by weight based on the aqueous content of the solution. miploying' sulfuric acid as the mineral acid, the free acid content is preferably maintained at 3 percent by weight basedpn Vthe aqueous content of the solution and the temperature of the solution is maintained within the range of from 1i5 to 55 C.

It will be' observed that the principles oi op= eration ofthe present invention are in direct contrast to the prior art sature-wr processes for the production of ammonium sulfatecrystals.v

In such prior art processes, the salt crystals are formed directly in and removed as such from the saturator. in the present invention the' conditions in the saturator are regulated to form a salt solution of controlled concentration without formation of crystalsin the saturator,4 the solution is withdrawn from the saturator and is then cooled and supersaturated under vacuum and the vsupersaturated solution is passed into contact .with crystalsv of the salt.

Referring to Figure Vl of the drawings, referv ence numeral i' designates generally anyA well known type f lay-product coke oven -hattery which `maybe of the horizontal type having uptake pipes 2 through which gas ilows iromthe individual coking chambers tocollector main il equipped with a plurality oi sprays (not shown) supplied with ammonia liquor pumpen-ity pump 5 from tank S through conduit l1. A portion oi the weak liquor ows from the pump through conduit t to storage tank it' from which it may be pumped by pump li to ammonia still i2 equipped with a xed lime leg i3 for freeing the ammonia from the liquor in a manner-'well mown inthe art.

The weak ammonia liquor collecting in the eollector main 8 hows through pipes i@ and lil to l decanter 2B in which tar is separated vir'oin the liquor and from which the' liquor owc to tenis t. Coke oven gas likewise ows through pi is and leaves the latter through oiltake pipe 22 which leads to primary'cooler 28 and a second,- ary cooler- 2H filled with any'suitable packing 5 material which causes intermixture oi the gas with cooling liquor sprayed into the tops of the coolers in a manner well known in the coke oven art. Cooling liquor ilows from the bottom of the coolers throughv conduits 25 to the decahter 2li.

The coke oven gas is drawnvthrough the collector main Vand coolers by an exhauster pump 21 driven in the customary manner by'a condensing steam engine 2t, discharging exhaustA steam through conduit 29 to barometric condenser 30.

type equipped with the usual barometric leg 3i, a seal 32, a water inlet 33 supplying coolingwater to the water jets of the condenser and suction device 3d for removing non-condensables from the condenser. Condensation of the steam by the cooling water in the condenser produces'a vacnum therein. If desired, an engine of Ylower horse power (than would normally be used in the installations involving customary saturators) operating at full capacity may be employed to drive 'the euhauster. Y

From the exhauster pump 2l, the coke oven gas ows through a tar precipitator 35 which maybe of the electrical type to reheater 36 where it is reheated, eV g., to a temperature between about mouia still i2 may be introduced into the coke oven gas through conduit si communicating with conduit 39 to augment the ammonia content and being regulated to bring the humidity of the gas 4Q to from. 'I0 to 100 peri-cent. From conduit 39 the coke oven gas passes through a saturator-type absorption apparatus designated as a whole by reference numeral 4i and the ammonia-'free gas is conducted thence through conduit d2, final cooler dit and light oil scrubbers N where it is cooled and scrubbed.

The saturator involves a lead lined reaction chamber @i5 equipped with a coke oven gas inlet or cracker pipe 46 extending downwardly end it provided with a luted lower edge @i9 extending somewhat, e. g., from l0 to 20 inches,

below the level of the solution in chamber 4B.' In order to prevent local supersaturation which ber dt, the saturator may be provided with an ixnpeller type agitator El located within tubular A member t2 situated beneath the coke oven gas The saturator chamber is provided with overdow outlet conduit 53 located. at the surface of the solution therein,v which conduit discharges through liquid seal 59 to pump 6B which circulates the solution through conduit 5l to the inlet of pump @il discharging into vaporizer or vacuum chammr 55. Vacuum chamber 55 communicates through conduit el with harometric condenser 30 which, as hereinabove described, is supplied with steam from steam engine 28; the harometric condenser serves to condense the exhaust steam from steam engine 28 as well as the vapors from vacuumv 'chamber t5, thus maintaining vacuum on 40 to 48 C. Ammonia and steam from the amhumidity of the gas and additional steam may be Y through the top thereof and having a ared lower would result in crystal formation in the cham-y inlet;y the agitator is mounted on shaft 64 ex- The barometric condenser is of the conventional y interim agitator.

vacuum chamber. In vacuum chamber 85, the

solution from saturator 4| is cooled and concentrated under. vacuum to a condition of metarstable supersaturation with respect to the salt 5,

and then passes downwardly through pipe 6l to the lower portion of crystallizing chamber I containing a suspension or bed of crystals of the salt and thence upwardly over these crystals, whereby the solution deposits the salt of supersaturation on the surfaces of the crystals causing them to increase in size. Crystals mixed with any .desired portion of liquor may be removed from the crystallizing 'chamber continuously' or from time to time through pipes 12, I3 and pump M to a slurry tank (not shown) from which they may ine fed to a centrifuge for separating the crystals from the liquor. The solution is recirculated from the upper portion of the crystallizing chamber through overflow conduit 'l5 through liquid seal 16 back to the saturator, -free acid, water and liquor separated. from the crystals in the centrifuge being added through `conduit 18. The crystallizing chamber may 'be drained when desired through outlet 19.

Figure 2 illustrates a modification of the apparatus involving a saturator $0 equipped with a coke oven gasinlet 8i in the form of a 'perforated ring. In this ligure, the crystallizing apparatus and other parts identical with those shown in Figure 1 are designated by the reference numerals employed in Figure 1. Circulation of the solution within the saturator is obtained by pumping solution from neai` the bottom ofrfthe saturator to the crystallizing apparatus through conduit 83 by pump 6 0 and recirculating the'solution from the crystallizlng chamber through conduits 85 and 8G through fluidrseals (not shown) torthe upper portion of the body of solution in the saturator. In this manner suillientV circulation of the saturator solution is effected to prevent excess local supersaturation and crystal tormation lin the saturator Iwithout employing an liquor separated from the crystals in the centri- Iuge may be introduced into the saturator of Figure 2 through conduits I8 and Il.

In carrying out 'the invention for the produc- Make-up acid, water and.

free sulfuric acid per liter is circulated by pump Blfto the inlet'of pump G3 which in tum discharges the solution into vacuum chamber or vaporizer 6l. Cooling of the solution in the conduits prior to reaching the vacuum chamber sumciently to promote crystal formation in the conduits should be avoided. If desired, these conduits may be insulated or steam-jacketed to prevent excesscooling.

'I'he .solution is cooled and concentrated under vacuum to a state of metasta-ble supersaturation and then passes through pipe 68 to the lower portion of crystallizing chamber 10 into contact with the bed or suspension of crystals in the chamber and ammonium sulfate from the solution deposits on the surfaces of the crystals causing them t0 grow, the larger crystals being removed through pipe 12 extending into the lower portion of the crystallizing chamber together with any desired proportion of liquor through pipe 73. Ammonium sulfate liquor at a temperature of about 43 to 53 C. and containing from about 43 to 46 per 'cent by weight of ammonium sulfate and from. about 10 to 50 grams of sulfuric acid per liter passes from the crystallizing chamber through overilow conduit 'l5 back to the upper portion of the saturator. Fresh acid, water and liquor separated from the crystals removed from the crystallizing chamber are introduced into the saturator through conduit 18 or conduits 88, 89, the` rates Y of introductionof the acid.: and water and the humidity of the coke oven gas 'being correlated to maintain the volume, acid and salt concentrain the saturator forms an acid seal through which' the coke oven gas bubbles upwardly so as to ac- -complish substantially complete removalof the 4i! ammonia from the gas. Y

tion of ammonium sulfate, for example, coke oven gas from collector main 3, coolers 23 and 24 and tar precipitator 35 is preheated in preheater 36, mixed with ammonia and steam from still l! and, if necessary, sunlcient additional steam is introduced through conduit 4l to raise the humidlty of the gas to about 98 per cent. `The gas at a temperature of about from 45" to 48 C. is

then introduced through the coke oven gas inlet beneath the surface of the saturator solution containing ab'out from 40 to 45 per cent by* weight of ammoniumsulfate andfrom 20 to grams o! free sulfuric acid per liter at a temperature of from 45 to 55? C. 4'I'he ammonia present in lthe gas reacts with the sint-uric acid in the solution t0 lform additional ammonium sulfate which in- Y.

creases lthe ammonium sulfate concentration of the solution but-not sumciently to promote crystal formation in the saturator. Sumcient circu V Coke oven gas free from ammonia escapes from the top of the saturator through pipe l2 and I passes through nal cooler 43 and light oil scrubbers Il.' In commencing operation, it is not necessary to begin with a solution of the ammonium salt' in the sazurator as absorption of ammonia in a solution of sulfuric or other mineral acid will in .due course result in a salt solution of n the desired concentration. i

In some cases incrustations of ammonium sulfate or other salt may tend to form on the walls of the saturator above the surface of the solution.

Such incrustations may be prevented or mini/7 mized by introducing` exhaust steam through steam linlet into the chamber above the'solution to increase the humidity of the gas leaving the saturator. vIf for any reason salt crystals or incrustations form in the saturator solution, they .mw be removed by raising the humidity of the coke oven gas to about'100 per centto minimize evaporation of water and increasing the rate of introduction of water sulciently to dissolve the incrustations. After the incrustatlons have been dissolved, operation as hereinabove described may be resumed.

In accordance with the invention, ammonium sulfate crystals oi' improved uniformity and sire as compared with those obtainable by thev cus-,-

tomary saturator process are produced. The crystals have the desirable characteristic that they-are less needle-like, i. e., that they are of greater thickness .in proportion to their length than crystals produced by certain saturator processes heretofore known. Since the coke oven gas inlet extends only from 10' to 20 inches below the suri'ace of the solution in the 1 saturator as compared with from about-'35 inches in the usual saturator process, less pressure is required to force thel coke oven gas through the apparatus in accordance with the invention, than is 'necessary in the usual saturator operations. The power thus saved may be utilized to produce the vacuum employed in supersaturating the solution with little or no increase in power costs. Furthermore. existing coke oven plants may be equipped to carry outA the invention without discarding the saturatcr chambers now employed in such plants.

Since certain changes may be made without departing from the scope of the invention, it is intended that the above should be interpreted as illustrative and not in a limiting sense. For example, while the invention is primarily intended for the production of ammonium salts from coke oven gas, it may be employed in the manufacture of such salts from other ammonia containing.

gases Aproduced in the carbonization of coal, e. g.,

z gases produced by the carbonization of coal in gas making retorts and producer gas produced from bituminous coal.

I claim: 1. A process for the recovery of ammonia fromammonia-containing gas .produced during the coking of coal as relatively large crystals of 'an taining an insumcient amount of ammonium sulfate to saturate the solution and suiiicient free sulfuric acid to absorb ammonia from said gas whereby the ammonia present in the gas reacts'o with the acid to form additional salt, continuously withdrawing solution from said saturato'r, cooling and concentrating they withdrawn solution to a condition ofmetastable supersaturation by evaporation under vacuum, passing the supersaturated solution into contact with a suspension of crystals' of ammonium sulfate whereby ammonium sul- ,Iate deposits from the solution on the surface oi and acid and the humidity of the coke oven gas ammonium salt of a mineral acid, which comprises heating said gas containing ammonia to a temperature within the range of to 66 C.,

adding sulcient moisture to the gas to raise its humidity to at least '70%, passing the humidiiied gas at a temperature within the range of 30 to 66 C. beneath the surface of a body of solution in e. saturator containing free mineral acidand an insufficient amount of ammonium salt of said acid to saturate said solution, whereby ammonia present in the gas reacts withthe acid to iorm -ariditional salt, withdrawing solution of said salt from said saturator, coolingand concentrating the withdrawn solution to a condition of metastable supersatura'tion by evaporation under vacuum,

. psing the supersaturated solution into contact with a suspension of crystals of said ammonium salt, whereby said salt deposits from the solution on thesurfaces of said crystals causing them to increase in size, recirculating the solution to said saturator, adding-water and free mineral-acid to lsaid saturator, correlating the rates of addition of water and acid and of recirculation of the solution to the'saturator and the humidity of the coke oven gas to prevent the ammonium sali; conucentrationof the solution in the saturator from risingabove saturation, and eieoting circulation of the solution within the 'saturator to prevent local supersaturation and crystal growth within to maintain a substantially constant temperature of from 45 to 55 C. and a substantially constant volume of solution in said saturator and to prevent the ammonium sulfate concentration of the solution in the saturator from rising above saturation, and effecting circulation of the solution within the saturator to prevent substantial local supersaturation and crystal the saturator.

3. A process for the recovery of ammonia as relatively large crystals .of ammonium sulfate which comprises passing preheated ammonia-l 30 containing coke oven gas at a regulated humidity o! atleast 'I0 per cent and a temperature of from 30 C. to 60 C. beneath the surface of a body of solution in a saturator containing insuilicient ammonium sulfate toisaturate the solution and free sulfuric acid whereby the ammonia present in the gas reacts with the sulfuric acid 'to form additional ammonium sulfate, withdrawing ammonium sulfate solution containing from 41 to 46 per cent by weight of ammonium sulfate and from oV 10 to 40`grams per liter of free sulfuric acid from said saturator, cooling and `concentrating the withdrawn solution tol a condition of metastable supersaturation with respect to ammonium sulfate 'by evaporation under vacuum, passing the metastable supersaturated solution upwardly through a suspension of crystals of ammonium sulfate whereby ammonium sulfate deposits from face ofv a body of solution in a saturatorcon- I said solution on the surfaces of said crystals causing them to increase in size, recirculating .the so'- lution containing from 43 to 46 per cent by weight of 'ammonium' sulfate and from 10 to 40 grams per liter of sulfuric acid at a temperature of-43 to 53 C. backito saidsaturatonadding suiiicient free sulfuric acid to said saturator to maintain the free acid concentration therein at from 20 to l grams per liter, adding water to said saturator and correlating the humidity of said coke oven sas and the rate of addition of water to maintain a substantially constant volume of said solution `in said saturator at a temperature within the range offrom'45 to 55 C., and to maintain the averageV ammonium sulfate concentration -in the saturator below the saturation point and efiecting circulation of the solution in the saturator to substantially prevent excessive local superssturation and formation of crystals in the body Of.

growth within' 

